Process of manufacturing surfactants and lubricants

ABSTRACT

A method of producing an alcohol ethoxylate surfactant or lubricant includes reacting a low molecular weight initiator with ethylene oxide in the presence of a polymerization catalyst, the low molecular weight initiator having a nominal hydroxyl functionality at least 1, and the polymerization catalyst being a Lewis acid catalyst having the general formula M(R 1 )1(R 2 )1(R 3 )1(R 4 ) 0 or 1 , whereas M is boron, aluminum, indium, bismuth or erbium, R 1 , R 2  and R 3  each includes a same fluoroalkyl-substituted phenyl group, and optional R 4  includes a functional group or functional polymer group. R 1 , R 2 , and R 3  are the same fluoroalkyl-substituted phenyl group. The method further includes forming the alcohol ethoxylate surfactant or lubricant having a number average molecular weight of greater than the number average molecular weight of the low molecular weight initiator in the presence of the Lewis acid catalyst.

FIELD

Embodiments relate to methods of manufacturing alcohol ethoxylatesurfactants and lubricants using at least a Lewis acid catalyst, alcoholethoxylate surfactants and lubricants prepared using at least the Lewisacid catalyst, and/or products/compositions that include the alcoholethoxylate surfactants and lubricants prepared using at least the Lewisacid catalyst.

INTRODUCTION

Polyether alcohols (i.e., polyols and monols) are produced bypolymerizing an alkylene oxide in the presence of a starter compound(also referred to as an initiator) and a catalyst. The starter compoundhas one or more functional groups the alkylene oxide can react with tobegin forming polymer chains. The starter compound may influence themolecular weight and establish the number of hydroxyl groups that theresultant polyether alcohol will have. Polyethers alcohols such asalcohol ethoxylates may be useful as, e.g., surfactants and lubricants.

Alcohol ethoxylates may be produced, e.g., by polymerizing at leastethylene oxide in the presence of a starter compound that is a C₆-C₂₄alcohol or a mixture of such alcohols and a catalyst. Various catalystsand process technologies have been developed to make commerciallyvaluable polyether alcohols, such as alcohol ethoxylate products.

With respect to the catalyst for forming polyether alcohols,manufacturing is moving toward the use of a double-metal cyanide (DMC)catalyst in place of an alkali metal catalyst (such as a KOH basedcatalyst). A disadvantage of DMC catalysts is that they are unable toefficiently polymerize ethylene oxide onto starter compounds, as taughtin U.S. Pat. No. 7,645,717. A further disadvantage of DMC catalysts isthat they may activate slowly, as is taught in U.S. Pat. No. 9,040,657.In particular, preparation of polyether polyols using the DMC catalystmay begin with a stage of the reaction known as the catalyst inductionperiod. During this stage of the reaction, the DMC catalyst is believedto become converted in situ from an inactive form into a highly activeform that rapidly polymerizes the alkylene oxide as long as the catalystremains active. This catalyst induction period is typically anindeterminate period of time following the first introduction ofalkylene oxide to the reactor. It is common to introduce a small amountof alkylene oxide at the start of the polymerization process and thenwait until the catalyst has become activated (as indicated, e.g., by adrop in reactor pressure due to the consumption of the initial alkyleneoxide that had been charged into the reactor) before continuing with thealkylene oxide feed. Very little or no polymerization occurs until thecatalyst has become activated, such that long activation times have adirect negative impact on the productivity of the process. It issometimes the case that the catalyst does not become activated at all.Such a failure of the catalyst to activate may result in the abandonmentof the attempt, and the process is started over again from thebeginning. As such, the activation process results in some loss ofproductivity under the best circumstances, and under the worstcircumstances can cause a loss of the entire batch of starting mixture.Thus, the reduction or elimination of the induction period at the startof the alkoxylation reaction is seen to be highly desirable.

Currently, base-catalyzed polymerization (e.g., KOH polymerization) isthe most commonly used ethoxylation process for alcohols. One problemoften seen in ethoxylating alcohols to make surfactant and lubricantproducts is low conversion of the alcohol starter compound. Insufficientalcohol conversion results in undesirable high unreacted alcohol residueleft in the final product. Alcohol residue in the final product maycause odor problem, may negatively impact the performance of product,and/or in extreme situations, may render the final product not useful.Low alcohol starter conversion may become more problematic when ahindered alcohol is used as the starter compound. Examples of hinderedalcohols include branched primary alcohols and linear or branchedsecondary alcohols. Secondary alcohols are particularly challenging tomake into quality alcohol ethoxylate surfactant and lubricant products.

Secondary alcohol ethoxylates may be useful as high performance nonionicsurfactants and lubricants, e.g., in multiple application areas. Due tothe relatively lower reactivity of the hydroxyl groups in a secondaryalcohol vs. primary hydroxyl group that is generated from ethylene oxidering opening during the polymerization, quality secondary alcoholethoxylate products typically cannot be manufactured by using abase-catalyzed ethoxylation process. When a base-catalyzed ethoxylationprocess is used for manufacturing a secondary alcohol, large portions ofthe starter compound may undesirably remain unreacted and the resultantethoxylated product may have a broad molecular weight distribution(e.g., based on high molecular ethoxylate components). Different fromlinear or branched primary alcohol ethoxylates, currently secondaryalcohol ethoxylate products are commercially produced by using atwo-step ethoxylation process, in which a secondary alcohol startercompound is first reacted with a small amount of ethylene oxide in thepresence of a Lewis acid catalyst, e.g. boron trifluoride, to get a lowEO adduct as an intermediate, from which various grades of ethoxylatedproducts are produced through a second base-catalyzed ethoxylationprocess. The complexity of the two step process may result in highmanufacturing cost of secondary alcohol ethoxylates. Accordingly, it isdesired that quality secondary alcohol ethoxylate products could beproduced through a one-step ethoxylation process.

DMC catalysts have been studied for one-step ethoxylation processes tomake secondary alcohol ethoxylate surfactants (e.g., see InternationalPublication No. WO 2012/071149). While the DMC catalyst cansignificantly increase alcohol starter conversion, the alcoholconversion rate by DMC may still not be sufficient to producecommercially viable secondary alcohol ethoxylate surfactants. Inaddition, DMC tends to generate high molecular polyethylene glycolby-products that cause hazy or precipitation problem in either the finalproduct and/or a formulated system that includes the final product.

The disadvantages of the use of conventional Lewis acid catalyst such asboron trifluoride alone to polymerize epoxides is well-known, e.g., astaught in U.S Pat. No. 6,624,321. The Lewis acids may significantlyincrease hindered alcohol starter conversion when compared toconventional base catalysts. However, a drawback associated with borontriflouride as an ethoxylation catalyst is the formation of dioxane. Itis believed that the dioxane is formed by degradation of polyethyleneoxide via oxonium salts, which also limits the attainable molecularweight of ethoxylation product. Certain Lewis acids, such as borontrifluoride, may be sensitive to the structure of alcohol startercompounds which may result in catalyst decomposition and release of ahighly corrosive HF side-product and incorporation of fluorine atoms inthe backbone of the polymerization product. This may require high levelsof catalyst loading which ultimately require the need for a laterprocess stage to remove catalyst from the resultant product. Further,boron trifluoride is regarded as hazardous material that is alsomoisture sensitive and difficult to handle.

The use of tris(pentafluorophenyl)borane catalyst during ring-openingpolymerization of an alkylene oxide is taught, e.g., in U.S. Pat. No.6,531,566. The tris(pentafluorophenyl)borane catalyst provides severaladvantages over conventional Lewis acids such as boron trifluoride. Forexample, the pentafluorophenylborane catalyst is not corrosive, easy tohandle, and appreciably more active. However, pentafluorophenylboranecatalyst produces an undesirable side-reaction leading to formation ofaldehydes and acetal linkages in the polyol backbone.

The use of a dual catalyst package for producing a polyol having a highprimary hydroxyl group content, which includes a DMC catalyst and aLewis acid catalyst such as tris(pentafluorophenyl)borane is disclosed,e.g., in International Publication No. WO 2016/064698. The DMC catalystenables the production of high molecular weight segments efficiently andthe Lewis acid catalyst enables the formation of primary hydroxyl endgroups. This method may minimize the residence time of the Lewis acidstep and therefore the amount of side-product.

A method of using a combination of DMC and KOH catalysts to produceEO-capped polyether polyols is taught, e.g., in U.S. Patent PublicationNo. 2011/0230581. In this process, the DMC catalyst is utilized topolymerize propylene oxide (PO) and KOH catalyst is utilized to promoteethylene oxide (EO) capping. This technology suffers from all thedrawbacks of conventional KOH technology, such as slow kinetics and needfor catalyst removal or finishing steps in the resultant polyetherpolyols.

A method of using a combination of tris(pentafluorophenyl)borane (Lewisacid) and KOH catalysts to product EO-capped polyether polyols is taughtin, e.g., U.S. Pat. No. 9,388,271. In this process, thetris(pentafluorophenyl)borane catalyst is utilized to polymerize PO in afirst step. During the first step, the vapor phase in the autoclave iscirculated through a reaction column and distillation column and back tothe autoclave reactor in order to minimize side-product formation. In asecond step, the KOH catalyst is utilized to polymerize EO onto the POchain ends. This process is complicated and may require finishingstep(s) to remove KOH catalyst residues.

In addition, many polyethers are block copolymers of propylene oxide andethylene oxide, or 1,2-butylene oxide and ethylene oxide. In such cases,when alkaline hydroxide or DMC catalysts are used, the terminalhydroxide for the polypropylene oxide block, or the polybutylene oxideblock, is a secondary alcohol. Just as in the ethoxylation of secondaryalcohol initiators, alkaline hydroxide, and DMC catalysts do not providebalanced ethoxylation of the polyol polyether since once a primaryalcohol is created from the initial conversion of the polyol polyether,these catalysts have more selectivity to further ethoxylate the alreadyethoxylated molecules over the unethoxylated molecules. This createsbroad dispersity in the amount of ethoxylation on the polyol polyethers,even to the point of some fraction of the polyol polyether having noethoxylation at all.

Therefore, improvements are sought with respect to producing an alcoholethoxylates surfactant or lubricant (such as a secondary alcoholethoxylate surfactant or lubricant) efficiently in such a way so as tonot require a catalyst removal step and/or to changing the selectivityof the Lewis acid catalyst itself, e.g., to improve yield of the desiredethylene oxide-based polyether alcohol product. Further, improvementsare sought with respect to a catalyst that can perform a one-stepethoxylation process on a hindered alcohol, e.g., a secondary alcohol,to produce useful alcohol ethoxylate surfactants, while minimizingand/or avoiding problems with the current process technologies asdescribed above. Also, improvements are sought with respect to acatalyst that can perform a one-catalyst alkoxylation with propyleneoxide and/or butylene oxide to form polymer intermediates followed byethoxylation of the polymer intermediates (e.g., where the polymerintermediates is a hindered alcohol such as a secondary alcohol), toproduce useful alcohol ethoxylate surfactants and lubricants, whileminimizing and/or avoiding problems with the current processtechnologies as described above.

SUMMARY

Embodiments may be realized by providing a method of producing analcohol ethoxylate surfactant or lubricant, the method includes reactinga low molecular weight initiator with ethylene oxide in the presence ofa polymerization catalyst, the low molecular weight initiator having anominal hydroxyl functionality at least 1, and the polymerizationcatalyst being a Lewis acid catalyst having the general formulaM(R¹)₁(R²)₁(R³)₁(R⁴)_(0 or 1), whereas M is boron, aluminum, indium,bismuth or erbium, R¹, R² and R³ each includes a samefluoroalkyl-substituted phenyl group, and optional R⁴ includes afunctional group or functional polymer group. The method furtherincludes forming the alcohol ethoxylate surfactant or lubricant having anumber average molecular weight of greater than the number averagemolecular weight of the low molecular weight initiator in the presenceof the Lewis acid catalyst.

DETAILED DESCRIPTION

Ethylene oxide (EO) is an important and widely used monomer in theproduction of alcohol ethoxylate surfactants and lubricants. EOpolymerization offers the opportunity to significantly increase thehydrophilicity and reactivity of the alcohol by virtue of the resultingprimary hydroxyl end groups. Homopolymers of EO such as certainpolyethylene glycols, may find limited use in certain applications asthey may crystallize readily and/or have a high affinity to water. Thehigh affinity of polyethylene glycols to water may be detrimental to theproperties of resultant products, e.g., as the products may be sensitiveto the humidity in the environment. The use of block structures formedby the addition of short EO segments (referred to as EO capping) to POalcohols has been proposed as a possible way to minimize difficultiesassociated with processability and water affinity. Another approach isto copolymerize EO and PO (e.g., mixed feed alcohols) to form alcoholsthat are composed of statistical mixtures of EO and PO.

Currently, alcohol ethoxylates are typically produced on an industrialscale utilizing KOH-catalyzed polymerization technology. Also, many havefound that DMC catalysts are typically unable to efficiently polymerizeEO at a commercial scale. The use of conventional Lewis acids topolymerize EO is not preferred due to side-reactions. For example, theseside-reaction may result in volatile side-products such as small cyclicethers and acetaldehyde. As a result the yield of the reaction may begreatly diminished. In addition, extra purification steps may be neededto obtain a product of sufficiently high quality. By yield it is meantherein percent yield, which is well-known as determined according to thefollowing equation:

% yield=(actual yield)/(theoretical yield)×100

As is well-known, the actual yield and theoretical yield may be based onweight percent or mole percent. The actual % yield is a dimensionlessnumber.

Further, as discussed in International Publication No. WO 2012/091968,certain Lewis acids that may essentially require no activation time havebeen evaluated as polymerization catalysts. However, some Lewis acidsmay become deactivated rapidly and may not be capable of producing highmolecular weight polymers or of obtaining high conversions of alkyleneoxides to polymer. Further, high amounts of alkaline catalysts, such assodium hydroxide may require treatment such as filtration and/or acidfinishing/neutralization (e.g., as discussed in U.S. Pat. No. 5,468,839)to reduce the base content of the resultant product. The use of asufficiently low amount of Lewis acid catalysts and optionally a DMCcatalyst may eliminate the need for such treatment, while also providingfor control and/or selectivity. However, certain Lewis acids may promoteundesirable side reactions. The presence of certain side products in analcohol product may necessitate performing an additional finishing stepon the resultant product.

Accordingly, embodiments relate to certain Lewis acid catalysts, andprocesses using such Lewis acid catalysts, that may provide advantageswith respect to minimizing side reactions such as those that produceundesired by-products and decrease yield of the desired products, whilestill allowing for precise control of the polymerization reaction. ByLewis acid it is meant a substance that can accept a pair of electrons.In other words, a Lewis acid in an electron-pair acceptor.

Embodiments may relate to providing alcohol ethoxylates having adesirable high yield, e.g., of EO capped polyether alcohols and/orpolyether alcohols prepared using a mixed feed of EO and anotheralkylene oxide. By EO capped alcohol it is meant polyether alcoholschains that have the addition of ethylene oxide (e.g., ethylene oxideonly and essentially excluding intended addition of any other alkyleneoxides such as propylene oxide and 1,2-butylene oxide) on at least oneend of such chain. EO capping may be performed on a polyether alcohol(e.g., derived from propylene oxide, ethylene oxide, and/or 1,2-butyleneoxide). EO capping may result in an alcohol product having a highprimary hydroxyl content (e.g., at least 30%, at least 40%, at least50%, at least 60%, at least 70%, at least 80%, etc.) For a mixed feedprocess, copolymerization EO and another alkylene oxide such aspropylene oxide may be performed on a starter compound and may result inan alcohol product having a higher primary hydroxyl content than thatprepared with a feed of propylene oxide alone.

During the polymerization process to form a polyether polyol, some Lewisacid catalysts such as the tris(pentafluorophenyl)borane catalyst, mayhave a disadvantage in that certain side reactions may occur atundesirable levels (depending on the outcome desired). An example ofsuch side reactions is the tris(pentafluorophenyl)boranecatalyst-assisted formation of acetaldehyde as shown below in Schematic1, which may occur in the presence of alcohols and may lead to the lackof desired chemoselectivity for the resultant polyether polyol. Further,high amount of formation of acetaldehyde or other volatile side-productsmay result in poor yield.

Further, a subsequent acetaldehyde-alcohol coupling reaction to form anacetal linkage, may result in higher molecular weight species, such asdimers, as compared to when the coupling is not present and/or may makemolecular weight control challenging especially at a commercial scale.Also, the water byproduct that results from the coupling reaction couldpotentially consume monomer and result in the formation of diols and/oralter the catalytic activity of the tris(pentafluorophenyl)boranecatalyst.

Accordingly, in exemplary embodiments, a reaction system for forming apolyether alcohol (such as an ethylene oxide based alcohol) uses a Lewisacid catalyst (e.g., in a low amount such that filtration and acidfinishing/neutralization are not required for the resultant polyetheralcohol) that minimizes side reactions and optionally may be combinedwith a DMC catalyst. For example, it is proposed to use triarylboranecatalysts that have fluoroalkyl-substituted phenyl groups, which mayallow for improvements with respect to selectively minimizing sidereactions so as to improve yield of desired EO based products and/or forprecise control of the polymerization reaction (such as an EO-cappingreaction).

In particular, it has been found that triarylborane catalysts containingfluoroalkyl substituents may significantly decrease the side-reactionsleading to lower acetal linkages in the backbone. It is believed thatthe fluoroalkyl groups may impart unique properties to the metal (suchas boron) active center. For example, the Hammett constant (σ) for afluorine group in the para position σ_(p)=0.06 whereas that for a CF₃group in the para position is 0.54. As such, a CF₃ group may act as aunique electron withdrawing group, which is in part related to theinability of F atoms to donate into the ring.

Embodiments relate to forming a polyether alcohol (e.g., an ethyleneoxide based alcohol) with a high yield and low amount of unreactedstarter compound. The polyether alcohol may have a low degree ofethoxylation. By degree of ethoxylation it is meant moles of EO per moleof starter. For example, the polyether alcohol may have a degree ofethoxylation that is less than 12 moles, greater than 2 moles, greaterthan 3 moles, greater than 5 moles, etc of EO per mole of starter. Thepolyether alcohol may have a relatively high number average molecularweight (i.e., greater than 500 g/mol, greater than 1000 g/mol, greaterthan 2,500 g/mol such as from 2,600 g/mol to 12,000 g/mol, 3,000 g/molto 6,000 g/mol, etc.) The polyether alcohol may have a specified primaryhydroxyl group content (e.g., from 30% to 90%, based on a total numberof hydroxyl groups). For example, the Lewis acid catalyst may be used toenable a desired amount of ethylene oxide capping for the resultantpolyether alcohol as a means toward achieving a desired primary hydroxylgroup content. Certain primary hydroxyl content values may be soughtafter for specific end use applications.

According to exemplary embodiments, a catalyst component for forming thepolyether alcohol may utilize the Lewis acid catalyst and optionally theDMC catalyst. For example, the Lewis acid catalyst may be used withoutthe DMC catalyst, or the DMC catalyst and the Lewis acid catalyst may besimultaneously or sequential added. For example, in a DMC-Lewis aciddual catalyst system, a polymerization method may include initiallyadding a DMC catalyst and later adding the Lewis acid catalyst that isseparately provided and allowed to react at a lower temperature than thetemperature at which the DMC catalyst was added. The Lewis acid catalystmay be active at a lower temperature range (e.g., from 60° C. to 115°C.) than a temperature range at which the DMC catalyst may be active(e.g., from 125° C. to 160° C.).

Polyether alcohols include polyols that have multiple ether bonds.Exemplary polyether alcohols include polyether hybrid alcohols (such aspolyether carbonate alcohols and polyether ester alcohols). Thepolyether alcohols are produced by polymerizing an alkylene oxidecomponent that includes at least one alkylene oxide and an initiatorcomponent that includes at least one initiator compound (i.e., startercompound). The initiator compound has one or more functional groups atwhich the alkylene oxide can react to begin forming the polymer chains.The main functions of the initiator compound are to providehydrophobicity and surface activity, molecular weight control and toestablish the number of hydroxyl groups that the monol or polyol productwill have. The polyether carbonate may be produced by polymerizingcarbon dioxide, at least one alkylene oxide, and an initiator compound.The polyether ester may be produced by polymerizing at least onealkylene oxide with a carboxylic acid initiator.

Lewis Acid Catalyst

According to exemplary embodiments, the Lewis acid catalyst has thegeneral formula M(R¹)₁(R²)₁(R³)₁(R⁴)_(0 or 1), whereas M is boron,aluminum, indium, bismuth or erbium, R¹, R², and R³ are each afluoroalkyl-substituted phenyl group, and optional R⁴ is a functionalgroup or functional polymer group. The M in the general formula mayexist as a metal salt ion or as an integrally bonded part of theformula. R¹, R², and R³ are each a fluoroalkyl-substituted phenyl group.R¹, R², and R³ are each the same fluoroalkyl-substituted phenyl group.

R¹, R², and R³ may include the fluoroalkyl-substituted phenyl group ormay consist essentially of the fluoroalkyl-substituted phenyl group.Similarly, R⁴ may include the functional group or functional polymergroup, or consist essentially of the R⁴ functional group or functionalpolymer group.

With respect to R¹, R², and R³, by fluoroalkyl-substituted phenyl groupit is meant a phenyl group that includes at least one hydrogen atomreplaced with a fluoroalkyl group, which is an alkyl group with at leastone hydrogen atom replaced with a fluorine atom. For example, thefluoroalkyl group may have the structure C_(n)H_(m)F_(2n+1−m), whereas nis greater than or equal to 1 and less than or equal to 5. Also, m is anumber that reflects a balance of the electrical charges to provide anoverall electrostatically neutral compound, e.g., can be zero, one orgreater than one. The phenyl group of the fluoroalkyl-substituted phenylmay be substituted to include other groups in addition to the at leastone fluoroalkyl group, e.g., a fluorine atom and/or chlorine atom thatreplaces at least one hydrogen of the phenyl group. For example, R¹, R²,and R³ may be a fluoro/chloro-fluoroalkyl-substituted phenyl group(meaning one fluoro or chloro group and at least one fluoroalkyl groupare substituted on the phenyl group),difluoro/chloro-fluoroalkyl-substituted phenyl group (meaning twofluoro, two chloro, or a fluoro and chloro group and at least onefluoroalkyl group are substituted on the phenyl group),trifluoro/chloro-fluoroalkyl-substituted phenyl group (meaning threefluoro, three chloro, or a combination of fluoro and chloro groupstotaling three and at least one fluoroalkyl group are substituted on thephenyl group), or tetrafluoro/chloro-fluoroalkyl-substituted phenylgroup (meaning four fluoro, four chloro, or a combination of fluoro andchloro groups totaling four and one fluoroalkyl group are substituted onthe phenyl group).

With respect to optional R⁴, the functional group or functional polymergroup may be a Lewis base that forms a complex with the Lewis acidcatalyst (e.g., a boron based Lewis acid catalyst) and/or a molecule ormoiety that contains at least one electron pair that is available toform a dative bond with a Lewis acid. The Lewis base may be a polymericLewis base. By functional group or functional polymer group it is meanta molecule that contains at least one of the following: water, analcohol, an alkoxy (examples include a linear or branched ether and acyclic ether), a ketone, an ester, an organosiloxane, an amine, aphosphine, an oxime, and substituted analogs thereof. Each of thealcohol, linear or branched ether, cyclic ether, ketone, ester, alkoxy,organosiloxane, and oxime may include from 2-20 carbon atoms, from 2-12carbon atoms, from 2-8 carbon atoms, and/or from 3-6 carbon atoms.

For example, the functional group or functional polymer group may havethe formula (OYH)n, whereas O is O oxygen, H is hydrogen, Y is H or analkyl group, and n is an integer (e.g., an integer from 1 to 100).However, other known functional polymer groups combinable with a Lewisacid catalyst such as a boron based Lewis acid catalyst may be used.Exemplary cyclic ethers include tetrahydrofuran and tetrahydropyran.Polymeric Lewis bases are moieties containing two or more Lewis basefunctional groups such as polyols and polyethers based on polymers ofethylene oxide, propylene oxide, and butylene oxide. Exemplary polymericLewis bases include ethylene glycol, ethylene glycol methyl ether,ethylene glycol dimethyl ether, diethylene glycol, diethylene glycoldimethyl ether, triethylene glycol, triethylene glycol dimethyl ether,polyethylene glycol, polypropylene glycol, and polybutylene glycol.

Exemplary Lewis acid catalysts have the following structure in whicheach of Ar¹ includes at least one fluoroalkyl (Y) group substituted on aphenyl group and optionally at least one fluoro or chloro (X)substituted on the phenyl group:

Whereas each Ar¹ has the same structure. Exemplary structures for Ar¹are the following, referred to as Set 1 structures:

According to exemplary embodiments, the Lewis acid catalyst is a boronbased Lewis acid catalyst that has the general formulaB(R¹)₁(R²)₁(R³)₁(R⁴)_(0 or 1), whereas R¹, R², and R³ are thefluoroalkyl-substituted phenyl group, and optionally R⁴ is thefunctional group or functional polymer group. For example, thefluoroalkyl-substituted phenyl group is a2,4-difluoro-3-(trifluoromethyl)phenyl group. For example, thefluoroalkyl-substituted phenyl group is a2,4,6-trifluoro-3-(trifluoromethyl)phenyl group. For example, thefluoroalkyl-substituted phenyl group is a3,5-difluoro-4-(trifluoromethyl)phenyl group. In exemplary embodiments,at least one of R¹ or R² or R³ is a 3,4- or3,5-bis(fluoroalkyl)-substituted phenyl group (e.g., a 3,4 or3,5-bis(trifluoromethyl)-substituted phenyl group). For example, R⁴ is acyclic ether having 3-10 carbon atoms.

Exemplary structures for the Lewis acid catalysts, where M is Boron areshown below:

While the above illustrates exemplary structures that include boron,similar structures may be used that include other metals such asaluminum, indium, bismuth, and/or erbium.

Without intending to be bound by this theory, certain R⁴ may helpimprove shelf life of the catalyst, e.g., without significantlycompromising catalyst activity when utilized in a polymerizationreaction. For example, the catalyst comprising M, R¹, R², and R³ may bepresent in the form with the optional R⁴ (form M(R¹)₁(R²)₁(R³)₁(R⁴)₁) orwithout the optional R⁴ (form M(R¹)₁(R²)₁(R³)₁). The optional R⁴ maydissociate step-wise from M(R¹)₁(R²)₁(R³)₁(R⁴)₁ to give freeM(R¹)₁(R²)₁(R³)₁, as shown below for M=B, which free M(R¹)₁(R²)₁(R³)₁may be a catalyst for an alkoxylation/polymerization process, and/or maydissociate from M(R¹)₁(R²)₁(R³)₁(R⁴)₁ in a concerted or othersingle-step process with the alkylene oxide to give a catalyst for analkoxylation/polymerization process.

For example, the catalyst including M, R¹, R², and R³ may be present inthe form with and without the optional R⁴ group, as shown below.

The ability of the optional R⁴ group to protect the boron, aluminum,indium, bismuth and erbium center from inadvertent decompositionreactions may be related to the decrease in the accessible volume of thecenter. The accessible volume of the center is defined as the volumearound the atom, such as boron atom, that is available for interactionwith a small molecule like a solvent molecule.

Accessible volume of Catalyst boron (%)

25

10

Suitable R⁴ groups that can help increase catalyst shelf stability,e.g., without compromising catalyst activity, include diethyl ether,cyclopentyl methyl ether, methyl tertiary-butyl ether, tetrahydrofuran,tetrahydropyran, 1,4-dioxane, acetone, methyl isopropyl ketone,isopropyl acetate, and isobutyl acetate.

The Lewis acid catalyst used in exemplary embodiments may be a blendcatalyst that includes one or more Lewis acid catalyst (e.g., eachhaving the general formula B(R¹)₁(R²)₁(R³)₁(R⁴)_(0 or 1)) and optionallyat least one other catalyst (such as catalyst known in the art forproducing polyether polyols). The blend catalyst may optionally includeother catalysts, in which Lewis acid catalysts having the generalformula account for at least 25 wt %, at least 50 wt %, at least 70 wt%, at least 75 wt %, at least 80 wt %, at least 85 wt %, at least 90 wt%, at least 95 wt %, at least 99 wt %, etc., of the total weight of theblend catalyst.

DMC Catalyst

The catalyst component may optionally include DMC catalysts. ExemplaryDMC catalysts and method of producing DMC catalyst are described, e.g.,in U.S. Pat. Nos. 3,278,457, 3,278,458, 3,278,459, 3,404,109, 3,427,256,3,427,334, 3,427,335, and 5,470,813. An exemplary type of DMC catalystis a zinc hexacyanocobaltate catalyst complex. The mDMC catalystcomplexes may be prepared using modified methods of forming the DMCcatalysts. The DMC catalyst, e.g., ones that are known in the art, maybe used in the catalyst system that includes the Lewis acid catalyst.The DMC catalyst may be the first or second catalyst that is provided.

For example, the DMC catalysts may be represented by the Formula 1:

M_(b)[M¹(CN)_(r)(X)_(t)]_(c)[M²(X)₆]_(d)·nM³ _(x)A_(y)  (Formula 1)

wherein M and M³ are each metals; M¹ is a transition metal differentfrom M. X¹ represents a group other than cyanide that coordinates withthe M¹ ion. M² is a transition metal. X² represents a group other thancyanide that coordinates with the M² ion. X¹ or X² may eachindependently be a halogen, sulfate, nitrate, phosphate, carbonate, orchlorate. In exemplary embodiments, X¹ and X² are the same and arechloride. A¹ represents an anion; b, c and d are numbers that reflect anelectrostatically neutral complex; r is from 4 to 6; t is from 0 to 2; xand y are integers that balance the charges in the metal salt M³_(x)A_(y), and n is zero or a positive integer. For example, n is from0.01 to 20. The foregoing formula does not reflect the presence ofneutral complexing agents such as t-butanol which are often present inthe DMC catalyst complex.

Referring to Formula (I), M and M³ each are a metal ion independentlyselected from (e.g., from the group consisting of): Zn²⁺, Fe²⁺, Co⁺²⁺,Ni²⁺, Mo⁴⁺, Mo⁶⁺, Al⁺³⁺, V⁴⁺, V⁵⁺, Sr²⁺, W⁴⁺, W⁶⁺, Mn²⁺, Sn²⁺, Sn⁴⁺,Pb²⁺, Cu²⁺, La³⁺ and Cr³⁺. Exemplary embodiments include at least Zn²⁺.Further, M¹ and M² each are a metal ion independently selected from(e.g., from the group consisting of): Fe³⁺, Fe²⁺, Co³⁺, Co²⁺, Cr³⁺,Cr³⁺, Mn²⁺, Mn³⁺, Ir³⁺, Ni²⁺, Rh³⁺, Ru²⁺, V⁴⁺V⁵⁺, Ni²⁺, Pd²⁺, and Pt²⁺.Among the foregoing, those in the plus-three oxidation state may be usedfor the M¹ and M² metal. Exemplary embodiments include Co⁺³ and/or Fe⁺³.

Suitable anions A include, but are not limited to, halides such aschloride, bromide and iodide, nitrate, sulfate, carbonate, cyanide,oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, analkanesulfonate such as methanesulfonate, an arylenesulfonate such asp-toluenesulfonate, trifluoromethanesulfonate (triflate), and a C₁₋₄carboxylate. Exemplary embodiments include the chloride ion.

Referring to Formula (I), r is an integer that is 4, 5 or 6. Inexemplary embodiments, r is 4 or 6. Further, t is an integer from 0 to2, and in exemplary embodiments t is 0. The sum of r+t may equal six.

In exemplary embodiments, the DMC catalyst is a zinc hexacyanocobaltatecatalyst complex. The DMC catalyst may be complexed with t-butanol. TheDMC catalyst used in exemplary embodiments may be a blend catalyst thatincludes of one or more DMC catalysts. The blend catalyst may optionallyinclude a non-DMC catalyst, in which the DMC catalysts account for atleast 75 wt % of the total weight of the blend catalyst. The blendcatalyst may exclude any of Lewis acid catalyst that is added at a latertime in the dual catalyst system.

Use of the Catalyst Component

In embodiments where the Lewis acid catalyst is used the alkoxylation oflow hydroxyl equivalent weight starter compounds, also referred to asinitiators, may proceed directly from the starter compound to a finishedpolyether alcohol by the polymerization of one or more alkylene oxides.Further, the use of the Lewis acid catalyst during the polymerizationreaction may reduce certain side reactions that lead to increasedpolydispersity and/or to increased acetal content in a final product.

The starter compound, also referred to as an initiator, has a lowmolecular weight such as less than 3,000 g/mol (e.g., less than 2,000g/mol, less than 1,000 g/mol, less than 500 g/mol, less than 250 g/mol,etc.) and a nominal hydroxyl functionality at least 1. The initiator isany organic compound that is to be alkoxylated in the polymerizationreaction. The initiator may contain as many as 8 or more hydroxylgroups. For example, the initiator may be a diol or triol. Mixtures ofstarter compounds/initiators may be used. The initiator will have ahydroxyl equivalent weight less than that of the polyether product,e.g., may have a hydroxyl equivalent weight of less than 333 g/molequivalence, less than 300 g/mol equivalence, from 30 to 300 g/molequivalence, from 30 to 250 g/mol equivalence, from 50 to 250 g/molequivalence, etc. The starter compound may be linear or branched. Thestarter compound may include primary and/or secondary hydroxyl group(s).

Exemplary initiator compounds include, but are not limited to, at leastone linear or branched alcohols such as secondary alcohols. Exemplaryinitiator compounds include, but are not limited to, ethylene glycols,diethylene glycols, triethylene glycols, propylene glycols, dipropyleneglycols, tripropylene glycols, butane diols, hexane diols, octane diols,cyclohexane dimethanols, glycerins, trimethylolpropanes,trimethylolethanes, pentaerythritols, sorbitols, sucroses, octanols,nonanols, decanols, undecanols, dodecanols, tridecanals, tetradecanols,pentadecanols, dexadecanols, tridecyls: as well as alkoxylates(especially ethoxylates and/or propoxylates) of any of these that have anumber average molecular weight less than that of the product of thepolymerization (e.g., less than 3000 g/mol). The exemplary initiatorcompounds include variants thereof, e.g., such as 2-decanol, 3-decanol,4-decanol, and 5-decanol. Other exemplary initiator compounds includerimethyl nonanol; methyl-, ethyl-, propyl-, butyl-, hexyl-, heptyl-,octyl-, nonyl-, and/or decyl-branched secondary alcohols. Otherexemplary initiator compounds include secondary alcohols derived fromhydrolysis of highly branched tripropylene, tetrapropylene, dibutylene,tributylene, and/or dihexene. In an exemplary embodiment, the startercompound may include a linear or branched secondary alcohol producedaccording to methods such as those described in U.S. Pat. No. 4,927,954.For example, the initiator compounds may include at least one detergentC8 to C16 range linear or branched secondary alcohol, such as2,6,8-trimethyl-4-nonanol, 2-octanol, or linear or branched C11-C15(e.g., C12-C14) secondary alcohol (or mixtures thereof).

The starter compound/initiator may be a low molecular weight polyetheralcohol that has been formed using an alkylene oxide such as propyleneoxide, ethylene oxide, and/or butylene oxide (e.g., which is polymerizedwith another starter compound/initiator). The starter compound may be adiol or triol. For example, the starter compound is an all propyleneoxide based diol or triol having a hydroxyl functional based equivalentweight of less than 333 g/mol equivalence and/or less than 300 g/molequivalence. In another example, the starter compound is an all ethyleneoxide based diol or triol having a hydroxyl functional based equivalentweight of less than 333 g/mol equivalence and/or less than 300 g/molequivalence

When the Lewis acid catalyst is used the temperature of the reactor maybe reduced at least 20 ° C. as compared to when the DMC catalyst isused. For example, the temperature for use of a DMC catalyst may be from125 ° C. to 160 ° C. (e.g., during a time at which an alkylene oxidefeed is gradually/slowly added to the reactor and after the time atwhich the starter compound is mixed with the DMC catalyst). Thetemperature for use of the Lewis acid catalyst may be from 25 ° C. to115 ° C. and/or from 60 ° C. to 115 ° C. (e.g., during a time at whichethylene oxide is feed to the reactor to form an EO-capped alcohol). Inexemplary embodiments, the control of the relative contribution of amixture containing an active DMC catalyst and an active Lewis acid mayenable the Lewis acid to dominate the addition of oxirane onto chainends.

In an exemplary embodiment, when the polyether alcohol is derived frompropylene oxide based initiator (e.g., a polyoxypropylene startercompound), during the polymerization process ethylene oxide may be addedto the reaction mixture to form the polyether alcohol having a numberaverage molecular weight of greater than the number average molecularweight of the initiator.

The polymerization reaction can be performed in any type of vessel thatis suitable for the pressures and temperatures encountered. In acontinuous or semi-continuous process the vessel may have one or moreinlets through which the alkylene oxide and additional initiatorcompound may be introduced during the reaction. In a continuous process,the reactor vessel should contain at least one outlet through which aportion of the partially polymerized reaction mixture may be withdrawn.A tubular reactor that has single or multiple points for injecting thestarting materials, a loop reactor, and a continuous stirred tankreactor (CSTR) are all suitable types of vessels for continuous orsemi-continuous operations. An exemplary process is discussed in U.S.Patent Publication No. 2011/0105802.

The resultant polyether alcohol product may be further treated, e.g., ina flashing process and/or stripping process. For example, the polyetheralcohol may be treated to reduce catalyst residues even though thecatalyst residue may be retained in the product. Moisture may be removedby stripping the alcohol. The polyether alcohol derived from ethyleneoxide, according to embodiments, may have a Lewis acid catalystconcentration (in ppm in the final polyoxypropylene alcohol) of from 50ppm to 1000 ppm (e.g., 100 ppm to 500 ppm and/or 100 ppm to 250 ppm).

The polymerization reaction may be characterized by the “build ratio”,which is defined as the ratio of the number average molecular weight ofthe polyether product to that of the initiator compound. This buildratio may be as high as 160, but is more commonly in the range of from2.5 to about 65 and still more commonly in the range of from 2.5 toabout 50. The build ratio is typically in the range of from about 2.5 toabout 15, or from about 7 to about 11 when the polyether product has ahydroxyl equivalent weight of from 85 to 400.

Exemplary embodiments relate to preparing the polyether polyols usingone or more of certain Lewis acid catalysts as polymerization catalyststhat may achieve a lower acetal content in the resultant polyetherpolyols (e.g., less than 5.0 mol %, less than 4.0 mol %, less than 3.0mol %, less than 1.5 mol %, less than 1.0 mol %, less than 0.8 mol %,less than 0.5 mol %, less than 0.2 mol % etc.), based on the total molesof carbon in the resultant polyol chains, while still producing highmolecular weight polyols (e.g., poly-ethylene oxide polyols,poly-propylene oxide/ethylene oxide polyols, poly-ethyleneoxide/butylene oxide polyols, etc.)

Exemplary embodiments related to preparing EO-capped polyether alcoholsat a high yield, e.g., a yield of at least 50 wt %, at least 60 wt %, atleast 70 wt %, at least 80 wt %, at least 90 wt %, at least 95 wt %,etc., based on a total weight of the resultant alcohol product.

Exemplary embodiments relate to using one or more of certain Lewis acidcatalyst as polymerization catalyst, such that use of the Lewis acidcatalyst may result in higher activation barriers to aldehyde formation,which is an undesired product, as compared to the activation barrier forforming the desired polyether polyol product or intermediate. As suchthe formation of the desired product or intermediate product may befavored during the polymerization process compared to the undesiredproducts. For example, the activation barrier to aldehyde formation maybe greater than 6.0 kcal/mol, greater than 7.0 kcal/mol, greater than8.0 kcal/mol, and/or greater than 9.0 kcal/mol. The activation barrierto aldehyde formation may be less than 30 kcal/mol and/or less than 20kcal/mol.

The alcohol ethoxylate surfactant or lubricant may be used in variousapplications. The alcohol ethoxylate surfactant or lubricant may be anadditive in a blended composition for use in various applications. Forexample, the alcohol ethoxylate surfactant may be used to increase thecleaning and wetting properties of household cleaners, to enhanceindustrial and institutional cleaning product formulations, tocontribute desired mechanical properties and/or storage stability toemulsion polymerization systems, in agricultural formulations, textileprocessing, paper manufacturing, oilfield operations, etc. The alcoholethoxylate lubricant may be used in numerous industrial applications,e.g., as thickening agent, for lubrication, foam control, heat transfer,plasticizers, solvents, etc. The alcohol ethoxylate surfactant orlubricant may be a secondary alcohol ethoxylate surfactant or lubricant,e.g., prepared using a secondary alcohol has an initiator. The alcoholethoxylates surfactant or lubricant may be linear or branched.

All parts and percentages are by weight unless otherwise indicated. Allmolecular weight values are based on number average molecular weightunless otherwise indicated.

EXAMPLES

Approximate properties, characters, parameters, etc., are provided belowwith respect to various working examples, comparative examples, and thematerials used in the working and comparative examples.

Catalyst Synthesis

The general production for catalyst synthesis is as follows. Unlessotherwise noted, all experimental procedures and manipulations ofchemical substances are performed in a nitrogen-purged glove box or on aSchlenk line. All bulk reaction solvents (toluene, diethyl ether,hexane, tetrahydrofuran (THF)) are dried by passage through columns ofalumina and Q5 reactive scavenger. All other solvents are purchased fromAldrich anhydrous grade and stored over activated 3 Å molecular sievesprior to use. NMR solvents (CDCl₃ and C₆D₆), obtained from CambridgeIsotope Laboratories, Inc., are dried over molecular sieves or, in thecase of C₆D₆, dried using Na/K alloy. Further,1-bromo-3,5-bis(trifluoromethyl)benzene, 1-bromo-2,4-difluoro-3-trifluoromethylbenzene, and 1-bromo-3,5-difluoro-4-trimethylbenzene arepurchased from Oakwood Chemical. Also,1-bromo-2,4,6-trifluoro-3-trifluoromethylbenzene, isopropylmagnesiumchloride-lithium chloride (solution in THF), and boron trifluoridediethyletherate) are obtained from Sigma-Aldrich and used as received.Further, isopropylmagnesium chloride lithium chloride complex (solutionin THF) is titrated before use using 1.00 M decanol in toluene with1,10-phenanthroline as an indicator.

Multinuclear NMR spectra (¹H, ¹³C, ¹⁹F) are collected on one of thefollowing instruments: Varian MR-400 or Varian VNMRS-500. The ¹H and ¹³CNMR chemical shifts are referenced in parts per million relative toresidual solvent peaks: ¹H—7.15 ppm for C₆D₆, 7.25 ppm for CDCl₃;¹³C—128.00 ppm for C₆D₆, and 77.00 ppm for CDCl₃. Boron-11 NMR chemicalshifts are referenced externally to BF₃(Et₂O) (0 ppm), and ¹⁹F NMRchemical shifts are referenced externally to CFCl₃ (0 ppm). Sub-ambientreaction temperatures, except when dry ice or ice were the sole means ofcooling, are measured using an Extech Instruments EasyView™10 Dual Kmodel EA 10 thermometer with a fine JKEM sensor PTFE wire K 36INJ.

Catalyst 1 is (tris(3,5-bis(trifluoromethyl)phenyl)borane).

Catalyst 2, is the THF adduct of Catalyst 1.

Catalyst 1 and 2 are prepared according to the following Schematic 2:

In particular, isopropylmagnesium chloride-lithium chloride (70.8 mL,87.0 mmol, 1.23 M solution in THF) is added to a solution of1-bromo-3,5-bis(trifluoromethyl)benzene (25.5 g, 87.0 mmol) in THF (250mL) which is in an acetone bath cooled with dry ice and held within atemperature range of between −35 ° C. to −25 ° C. during the addition.After the addition is complete, the reaction flask is transferred to anice bath (0 ° C.) and the reaction mixture is stirred for 3 hours. Thereaction mixture is cooled to about −35 ° C. and boron trifluoridediethyletherate (4.26 mL, 29.0 mmol) is added while maintaining thereaction mixture at a temperature range of between −35 ° C. to −25 ° C.The reaction mixture is allowed to warm to room temperature while it isstirred overnight. The resultant ¹⁹F NMR spectra of the reaction mixtureshows a major peak (95%) at δ −63.2 and a minor peak (5%) at δ −63.7corresponding to 1-bromo-3,5-bis(trifluoromethyl)benzene. Next, the THFis removed from the reaction mixture under reduced pressure. The residueis extracted with toluene and filtered using several PTFE frits becausethe very fine precipitate may be difficult to filter. The volatiles areremoved under reduced pressure to give a very viscous oil. A portion ofthe product (about ⅔ to ¾) is put in a sublimator and sublimed (bystarting at 80 ° C. and gradually increasing the temperature to 150 ° C.over several days in an oil bath under ≤1 mtorr vacuum) to give 3.95grams (6.07 mmol, 21%) of white solid on the sublimator finger. Smallcrystals may also be present. This material is characterized bymultinuclear NMR spectroscopy as Catalyst 1. Additional, less pure,product is scraped out of the top portion of the sublimator body, in anamount of 2.01 grams. The less pure material, which by NMR ischaracterized as a 2:1 mixture of borane to THF, is dissolved in THF,filtered, and the volatiles are removed under reduced pressure. Thismaterial is characterized by multinuclear NMR spectroscopy as Catalyst 2(2.00 g, 2.77 mmol, 9.5%) Total yield: 6.07 mmol Catalyst 1 and 2.77mmol Catalyst 2 (30% overall yield).

Catalyst 3 is the THF adduct oftris(2,4-difluoro-3-(trifluoromethyl)phenyl)borane and is preparedaccording to Schematic 3:

In particular, isopropylmagnesium chloride-lithium chloride (15.6 mL,19.2 mmol, 1.23 M solution in THF) is added to a solution of1-bromo-2,4-difluoro-3-trifluoromethyl-benzene (5.00 g, 19.2 mmol) inTHF (100 mL) which is in an acetone bath cooled with dry ice and heldwithin a temperature range of between −35 ° C. to −25 ° C. during theaddition. After the addition is complete, the reaction flask istransferred to an ice bath (0 ° C.) and the reaction mixture is stirredfor 3 hours. The reaction mixture is cooled to about −35 ° C. and borontrifluoride diethyletherate (0.79 mL, 6.4 mmol) is added whilemaintaining the reaction mixture at a temperature range of between −35 °C. to −25 ° C. The reaction mixture is allowed to warm to roomtemperature while it is stirred overnight. Next, the THF is removed fromthe reaction mixture under reduced pressure. The residue is extractedwith toluene and filtered using a PTFE frit. The volatiles are removedfrom the filtrate under reduced pressure to give the product, the THFadduct of tris(2,4-difluoro-3-(trifluoromethyl)phenyl)borane.

Catalyst 4 is the THF adduct oftris(3,5-difluoro-4-(trifluoromethyl)phenyl)borane and is preparedaccording to Schematic 4:

In particular, isopropylmagnesium chloride-lithium chloride (31.1 mL,38.3 mmol, 1.23 M solution in THF) is added to a solution of1-bromo-3,5-difluoro-4-trifluoromethylbenzene (10.0 g, 38.3 mmol) in THF(150 mL) which is in an acetone bath cooled with dry ice and held withina temperature range of between −35 ° C. to −25 ° C. during the addition.After the addition is complete, the reaction flask is transferred to anice bath (0 ° C.) and the reaction mixture is stirred for 3 hours. Thereaction mixture is cooled to about −35 ° C. and boron trifluoridediethyletherate (1.58 mL, 12.8 mmol) is added while maintaining thereaction mixture at a temperature range of between −35 ° C. to −25 ° C.The reaction mixture is allowed to warm to room temperature while it isstirred overnight. Next, the THF is removed from the reaction mixtureunder reduced pressure. The residue is extracted with toluene andfiltered using a PTFE frit. The volatiles are removed from the filtrateunder reduced pressure to give the product, the THF adduct oftris(3,5-difluoro-4-(trifluoromethyl)phenyl)borane.

Catalyst 5 is the THF adduct oftris(2,4,6-trifluoro-3-(trifluoromethyl)phenyl)borane and is preparedaccording to Schematic 5:

In particular, isopropylmagnesium chloride-lithium chloride (5.9 mL, 7.3mmol, 1.23 M solution in THF) is added to a solution of1-bromo-2,4,6-trifluoro-3-trifluoromethylbenzene (2.00 g, 7.17 mmol) inTHF (50 mL) which is in an acetone bath cooled with dry ice and heldwithin a temperature range of between −35 ° C. to −25 ° C. during theaddition. After the addition is complete, the reaction flask istransferred to an ice bath (0 ° C.) and the reaction mixture is stirredfor 3 hours. The reaction mixture is cooled to about −35 ° C. and borontrifluoride diethyletherate (0.30 mL, 2.4 mmol) is added whilemaintaining the reaction mixture at a temperature range of between −35 °C. to −25 ° C. The reaction mixture is allowed to warm to roomtemperature while it is stirred overnight. Next, the THF is removed fromthe reaction mixture under reduced pressure. The residue is extractedwith toluene and filtered using a PTFE frit. The volatiles are removedfrom the filtrate under reduced pressure to give the product, the THFadduct of tris(2,4,6-trifluoro-3-(trifluoromethyl)phenyl)borane.

Catalyst A is Tris(pentafluorophenyl)borane, also referred to as FAB,available from (available from Boulder Scientific).

Catalyst B is Boron Trifluoride Diethyl Etherate, also referred to asBF₃ (available from Sigma Aldrich).

Catalyst C is Potassium Hydroxide obtained with 10% water content, alsoreferred to as KOH (available from Sigma Aldrich)

Preparation of Alcohols

For preparing the alcohols, the following materials are principallyused:

Starter 1 A starter compound that is 2,6,8-trimethyl-4-nonanol, alsoreferred to as TMN (available from Sigma-Aldrich Corporation). Solvent Aglycol diether that has no hydroxyl functionality (available from TheDow Chemical Company as PROGLYDE ™ DMM). Additive An acidifying agentthat includes phosphoric acid. Magnesium A salt (available fromSigma-Aldrich Corporation). Silicate

In particular, the following reaction may be carried out in a continuousflow reactor using Catalysts 1 to 5 as discussed above. The reactionsmay be carried out in a manner shown below in exemplary Schematic 6, andin view of the conditions provided in Table 1:

The alcohols of Working Examples 1 to 5 and Comparative Examples B and Cmay be prepared using Starter 1 as the initiator, ethylene oxide (EO) asthe monomer, and the Solvent according to the conditions outlined inTable 1, below. Referring to Table 1, the EO binding enthalpy, andactivation barrier to aldehyde are determined according to thecomputational methods discussed below.

TABLE 1 EO Activation Catalyst binding barrier to Con. Time Tempenthalpy aldehyde Catalyst (ppm) (Min) (° C.) (kcal/mol) (kcal/mol) Ex.A — — 10 90 n/a n/a Ex. B A 1000 10 90 −6.0 5.3 Ex. C 20 Ex. 1 1 1000 1090 −3.7 8.7 Ex. 2 20 Ex. 3 2 1000 10 90 Ex. 4 3 1000 10 90 −5.7 6.2 Ex.5 4 1000 10 90 −6.8 9.9

Comparative Example A is a negative control that may be run withoutcatalyst. This example may be carried out by mixing the initiator andethylene oxide in the tubular reactor at 90 ° C. for 10 min

The alcohol samples for Working Examples 1 to 5 and Comparative ExamplesB and C, may be prepared in a continuous flow reactor that is amicroreactor available from Vapourtec Inc. For the examples, neat EOmonomer is fed to a pump via a pressure cylinder at 50 psig. A solventreservoir containing the Solvent is connected to another pump. A 2 mLinjection loop is utilized to introduce a solution of the specifiedcatalyst and initiator (as 60 wt % of P390 in dipropylene glycoldimethyl ether) into the system. By controlling the flow rate, thecatalyst and starter are introduced into the flow system at a definedrate. The EO monomer and initiator-catalyst-Solvent solution arecombined at a mixing unit and fed into a 2 mL stainless steel coiledreactor. A back pressure regulator set at 250 psig is used to controlthe system pressure and assist the EO to remain in a liquid phase. Thecontinuous pressure reactor is charged with 0.1 mL/min of theinitiator-catalyst-Solvent mixture. The ethylene oxide may be fed to thereactor at a constant feed rate of 0.1 mL/min. Once theinitiator-catalyst-Solvent mixture is introduced into the sample loop,the first 5.13 mL of the product mixture is diverted to a scrubberconsisting of 3 wt % aqueous potassium hydroxide. The next 3.04 mL ofproduct mixture may be collected and analyzed by MALDI spectrometry.

The Temperature in Table 1 is the temperature in the reactor. The Timeis residence time, which is defined as follows:

$\text{residence~~time} = \frac{\text{reactor~~volume}}{\begin{pmatrix}{{\text{flow~~rate~~of~~pump}\mspace{14mu} A} +} \\{\text{flow~~rate~~of~~pump}\mspace{14mu} B}\end{pmatrix}}$

When the flow rates of pumps A and B are 0.1 mL/min,

$\text{residence~~time} = {\frac{2\mspace{14mu} {mL}}{\left( {0.1 + 0.1} \right)\mspace{14mu} {mL}\text{/}\min} = {10\mspace{14mu} \min}}$

When the flow rates of pumps A and B are 0.05 mL/min,

$\text{residence~~time} = {\frac{2\mspace{14mu} {mL}}{\left( {0.05 + 0.05} \right)\mspace{14mu} {mL}\text{/}\min} = {20\mspace{14mu} \min}}$

The number-average molecular weight (Mn) achieved in the polymerizationreaction may depend on the amount of volatile side-products (e.g.acetaldehyde) formed. For example, higher levels of volatileside-products may result in a Mn that is significantly lower than thetheoretical Mn. Conversely, low levels of volatile side-products mayhelp achieve a Mn that is close to the theoretical Mn. It may bedesirable to achieve a Mn that is close to the theoretical Mn.

The PDI is defined as the ratio of the weight-average molecular weight(Mw) to the number-average molecular weight (Mn). The PDI may representa measure of the extent of acetal coupling, as this reaction mayeffectively double the molecular weight. Accordingly, a comparison ofthe PDI at similar Mn values may provide a measure of the selectivity ofa catalyst for alkoxylation (intended reaction) versus isomerization andacetalization. Lower PDI may be preferable for higher chemoselectivity.

The EO binding enthalpy is calculated relative to a resting stateconsisting of the free catalyst (where R⁴ is not present) and EO.Favorable binding (higher negative values, for example greater than −3.0kcal/mol, greater than −5.0 kcal/mol, etc) is preferable for higheractivity. Referring to Table 1, it is seen that calculations onCatalysts 1 to 4 provide a favorable EO binding enthalpy such thatfavorable activity is realized. Another measure of activity is the ringopening barrier shown below. Lower ring opening barriers are preferablefor higher activity.

The activation barrier to aldehydes determines the amount of aldehydeand acetal formed, as shown below. Higher activation barriers arepreferable for lower levels of aldehyde and subsequent acetal formation.

Referring to Working Examples 1 to 5 and Comparative Examples B and C,it is found that the activation barrier to undesired products (incomparison to the activation barrier for the desired EO contentpolyether polyol) is significantly higher for Catalysts 1 to 4 comparedto Catalyst A. As such, it is unexpectedly found that the structures ofCatalysts 1 to 4 may allow for increased yield of the desired product,as compared to Catalyst A.

Additional, Working Example 6 and Comparative Example D, E, and F arecarried out in a semi-batch process using Starter 1 and EO, using theCatalysts 2, A, B, and C.

Referring to Table 2, Theo Mn refers to the theoretical number averagemolecular weight defined as:

${Mn} = \frac{\text{Mass~~of~~Initiator} + {\text{Mass~~of~~Monomer}\mspace{14mu} (s)}}{\text{Moles~~of~~Initiator}}$

Referring to Table 2, GPC Mn refers to the number average molecularweight measured by GPC, Dioxane refers to the amount of 1,4-dioxane inthe product, Unreacted SM refers to the percentage of peak areacorresponding to Starter 1 in the GPC chromatogram, and Dimer refers tothe percentage of peak area corresponding to a molecular weight which istwice the GPC M_(n). The GPC Mn, Unreacted SM, Dioxane, and Dimer aredetermined according to the analytical methods discussed below.

TABLE 2 Un- Di- Cata- Temp Theo GPC reacted oxane Init Mon lyst (° C.)Mn Mn SM (ppm) Dimer Ex. Starter EO B 50 450 562 5.9 16796 — D 1 Ex.Starter EO C 120 362 1034 16.6 307 — E 1 Ex. Starter EO A 50 443 431 5.22629 14 F 1 Ex. Starter EO 2 50 522 415 4.7 687 8 6 1

For the semi-batch process, a semi-batch pressure reactor configurationequipped with a pneumatically driven impeller, thermocouple, coolingwater coils, a dip tube (¼″ inch OD) that is connected to a nitrogenline, monomer feed line and a vent using a four-way Swagelok fitting,and an aluminum heating block, is used. Starter 1 was dried bydistillation to <100 ppm water and stored under nitrogen to be used forComparative Example F and Working Example 6.

For Comparative Example D, a 2 L pressure reactor was charged with101.36 g of Starter 1. The reactor was sealed, pressure checked, purgedwith nitrogen, then a headspace port was opened and 0.65 g of Catalyst Bwas added using a syringe. The system was sealed and heated to 50 ° C.for the addition of 143.6 g of EO at an addition rate of 1 g/min. Afterholding for one hour at 50 ° C., the mixture was cooled to 30 ° C. andcollected (242.4 g, 99%). The clear solution was mixed with 10.0 g ofMagnesium Silicate and 2.06 g of water, and vacuum filtered to generate218.81 g of clear filtrate.

For Comparative Example E, a 250-mL round bottom flask was charged with136.32 g of Starter 1, 1.30 g of Catalyst C, and 0.5 mL of water. Thesolution was heated under a vacuum of 8 torr to a pot temperature of upto 111 ° C. to collect 17.23 g of distillate at a head temperature of upto 96 ° C. The base content was measured at 1.04 wt % (as Catalyst C). A2 L pressure reactor was charged with 89.88 g of this solution, and thereactor was sealed, pressure checked, purged with nitrogen, and thenheated to 120 ° C. for the addition of 128.6 g of EO at an addition rateof 2 g/min The reaction product was held at 120 ° C. for one hour to aconstant pressure, then cooled to 80 ° C. to unload 213.45 g. The warmliquid product was mixed with 10.0 g of Magnesium Silicate and 2.0 g ofwater, and vacuum filtered to afford 186.84 g of a light brown productwhich solidified upon cooling.

For Comparative Example F, Starter 1 (51.35 g) was transferred viasyringe to a dry reactor under positive nitrogen pressure and thereactor was heated to 50 C with stirring. Catalyst A (72.6 mg) wasdissolved in 1 mL of dry THF and transferred to the reactor via syringe.Three cycles of pad/de-pad were used to ensure an inert environment inthe reactor after catalyst addition. Ethylene oxide (72.751 g) was fedto the reactor subsurface at 0.75 g/min. Upon completion of oxide feed,the reactor was blocked in and allowed to digest until a constantpressure of <0.3 psi change over 10 minutes was observed. The reactorwas subsequently vented and the product was collected (111.09 g, 89.5%).

For Working Example 6, Starter 1 (52.2 g) was transferred via syringe toa dry reactor under positive nitrogen pressure and the reactor washeated to 50 C with stirring. Catalyst 2 (71.8 mg) was dissolved in 1 mLdry THF and transferred to the reactor via syringe. Three cycles ofpad/de-pad were used to ensure an inert environment in the reactor aftercatalyst addition. Ethylene oxide (74.4 g) was fed to the reactorsubsurface at 0.75 g/min. Upon completion of oxide feed, the reactor wasblocked in and allowed to digest until a constant pressure of <0.3 psichange over 10 minutes was observed. The reactor was subsequently ventedand the product was collected (107.7 g, 84.0%).

For Working Example 7, Starter 1 (52 g) was transferred via syringe to adry reactor under positive nitrogen pressure and the reactor was heatedto 50 C with stirring. Catalyst 3 (70 mg) was dissolved in 1 mL dry THFand transferred to the reactor via syringe. Three cycles of pad/de-padwere used to ensure an inert environment in the reactor after catalystaddition. Ethylene oxide (75 g) was fed to the reactor subsurface at0.75 g/min. Upon completion of oxide feed, the reactor was blocked inand allowed to digest until a constant pressure of <0.3 psi change over10 minutes was observed. The reactor was subsequently vented and theproduct was collected.

For Working Example 8, Starter 1 (52 g) was transferred via syringe to adry reactor under positive nitrogen pressure and the reactor was heatedto 50 C with stirring. Catalyst 4 (70 mg) was dissolved in 1 mL dry THFand transferred to the reactor via syringe. Three cycles of pad/de-padwere used to ensure an inert environment in the reactor after catalystaddition. Ethylene oxide (75 g) was fed to the reactor subsurface at0.75 g/min. Upon completion of oxide feed, the reactor was blocked inand allowed to digest until a constant pressure of <0.3 psi change over10 minutes was observed. The reactor was subsequently vented and theproduct was collected.

For Working Example 9, Starter 1 (52 g) was transferred via syringe to adry reactor under positive nitrogen pressure and the reactor was heatedto 50 C with stirring. Catalyst 5 (70 mg) was dissolved in 1 mL dry THFand transferred to the reactor via syringe. Three cycles of pad/de-padwere used to ensure an inert environment in the reactor after catalystaddition. Ethylene oxide (75 g) was fed to the reactor subsurface at0.75 g/min. Upon completion of oxide feed, the reactor was blocked inand allowed to digest until a constant pressure of <0.3 psi change over10 minutes was observed. The reactor was subsequently vented and theproduct was collected.

Referring to Table 2, it is seen that the residual starting material isless when Catalyst 2 is used, as compared to Catalyst C. As a result,the actual number average molecular weight as measured by GPC issignificantly closer to the theoretical number average molecular weightfor Working Example 6, as compared to Comparative Example E. The dioxanecontent of the product formed with Catalyst 2 is significantly reduced,as compared to the dioxane contents of the products formed withCatalysts A and B. The area of the dimer peak in Working Example 6 isless than Comparative Example F.

A process for the preparation of a polyether polyol may be carried outin a continuous or semi-batch process using a sequential dual catalystprocess, similar to International Publication No. WO 2016/064698, whichis incorporated by reference.

The analytical methods used with respect to the examples are describedbelow:

Determination of M_(n) for semibatch products: Gel PermeationChromatography (GPC) analysis is used for determination of numberaverage molecular weight (Mn), which is carried out at a flow rate of1.0 mL/min using four PLgel organic GPC columns connected in series (3μm, Agilent Inc.) and tetrahydrofuran as eluent. The column temperatureis 40 ° C. VORANOL™ CP 6001, VORANOL™ 210, 230-660, and 230-056N areused as standards.

Determination of residual starting material and dioxane content byGC-FID-MSD: Samples were prepared by dilution of the polyol samples 1:4by weight with dichlorobenzene. A gas chromatography method withsimultaneous flame ionization detection and mass selective detection(GC-FID-MSD) was developed. The method uses an Agilent HP-5 (30 m×0.32mm×0.25 um) employed in a 7890A Agilent GC with standard FID and anAgilent 5975C inert MSD with Triple-Axis Detector (350 ° C. capable).The column effluent was split between FID and MSD. The vacuum flowthrough the MSD is controlled via a restrictor line (0.45 m×0.1 mm×0 μm)to give a flow of 0.75 mL/min The rest of the effluent goes to the FIDunrestricted at 1.75 mL/min. Quantitation values were based on the FIDchromatogram and identification of peaks were derived from the MSspectra of component and matched to the NIST MSD library.

Computational Methodology for determination of binding enthalpy andactivation barrier to aldehyde: The structures of species in ground andtransition states are optimized using Density Functional Theory (DFT) atB3LYP/6-31g** level. The effect of dielectric medium is included byusing conductor like polarizable continuum model (CPCM), wherediethylether (ε=4.2) is used as the medium of choice. The vibrationalanalysis on the ground state geometries is performed and the lack ofimaginary frequencies is used to ascertain the minima in the potentialenergy surface (PES). On the other hand, the same analysis on thetransition state geometries indicated one imaginary frequency. In thelatter case, the GaussView program is used to visualize the vibrationalmode with imaginary frequency in order to ensure that the atoms movedalong the desired reaction coordinate. For both ground-state andtransition state geometries, the vibrational analysis is used to computethe enthalpy (H₂₉₈) at 298 K by augmenting zero point energy to theelectronic energy. For both ground state and transition state, variousconformations were explored and the enthalpy of the lowest conformationwas used to calculate binding and the barrier height for aldehydeformation. These calculations were performed using G09 suit of programs.

Computational determination of free (or accessible) volume: Once theoptimized geometry of free catalysts (where the catalyst is not bound tothe optional R⁴ Lewis base) or coordinated complexes (where a catalystis bound to the optional R⁴ Lewis base) are obtained using the abovemethod, a sphere of radius 3.0 Å is placed around the B atom (the volumeof this sphere is denoted as V1). This is followed by placing spheres onother atoms; the radii of these spheres are chosen to be the van derWaals radii of respective atoms. The volume of the sphere centered on Bwhich is occluded by spheres on other atoms is computed using a MonteCarlo integration technique. The occluded volume is represented as V2.The free volume (FV) is calculated using the following equation:

FV=1−(V2/V1)

The FV descriptor varies between 0 and 1. This technique is implementedusing Pipeline Pilot tool kit. This procedure is used in literature tounderstand bond dissociation trends.

1. A method of producing an alcohol ethoxylate surfactant or lubricant,the method comprising: reacting a low molecular weight initiator withethylene oxide in the presence of a polymerization catalyst, the lowmolecular weight initiator having a nominal hydroxyl functionality atleast 1, and the polymerization catalyst being a Lewis acid catalysthaving the general formula M(R¹)₁(R²)₁(R³)₁(R⁴)_(0 or 1), whereas M isboron, aluminum, indium, bismuth or erbium, R¹, R² and R³ each includesa same fluoroalkyl-substituted phenyl group, and optional R⁴ includes afunctional group or functional polymer group; and forming the alcoholethoxylate surfactant or lubricant having a number average molecularweight of greater than the number average molecular weight of the lowmolecular weight initiator in the presence of the Lewis acid catalyst.2. The method as claimed in claim 1, wherein the Lewis acid catalyst hasthe general formula M(R¹)₁(R²)₁(R³)₁(R⁴)_(0 or 1), whereas M is boron,and each of R¹, R², and R³ is a 3,4- or 3,5-bis(fluoroalkyl)-substitutedphenyl group.
 3. The method as claimed in claim 1, wherein the Lewisacid catalyst has the general formula M(R¹)₁(R²)₁(R³)₁(R⁴)_(0 or 1),whereas M is boron, and each of R¹, R², and R³ is afluoro/chloro-fluoroalkyl-substituted phenyl group,difluoro/chloro-fluoroalkyl-substituted phenyl group,trifluoro/chloro-fluoroalkyl-substituted phenyl group, ortetrafluoro/chloro-fluoroalkyl-substituted phenyl group.
 4. The methodas claimed in claim 1, wherein the Lewis acid catalyst has the generalformula M(R¹)₁(R²)₁(R³)₁(^(R4))¹.
 5. The method as claimed in claim 4,wherein R⁴ is a cyclic ether having 3-10 carbon atoms.
 6. The method asclaimed in claim 4, wherein R⁴ is a ketone having 3-10 carbon atoms. 7.The method as claimed in claim 1, wherein the low molecular weightinitiator is a secondary alcohol and the alcohol ethoxylate surfactantor lubricant is a secondary alcohol ethoxylate surfactant or lubricant.8. The method as claimed in claim 1, wherein the low molecular weightinitiator is a secondary alcohol having a number average molecularweight of less than 3,000 g/mol and the alcohol ethoxylate surfactant orlubricant is a secondary alcohol ethoxylate surfactant or lubricant. 9.An alcohol ethoxylate surfactant or lubricant prepared using the methodas claimed in claim
 1. 10. A composition that includes the alcoholethoxylate surfactant or lubricant prepared using the method as claimedin claim 1.